Puncture resistant tire

ABSTRACT

A tire and methods of manufacture thereof comprising a tire body and a metal reinforcing strip comprising at least one metal alloy foil layer to provide puncture resistance, wherein the at least one metal alloy foil layer comprises a spinodal glass matrix microconstituent structure.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. provisional patent applicationNo. 61/449,335 filed Mar. 4, 2011, the teachings of which areincorporated herein by reference.

FIELD OF INVENTION

The present application relates to a puncture resistant bicycle tireand, in particular, bicycle tires incorporating one or more layers ofmetal alloy foil exhibiting spinodal glass matrix microconstituents.

BACKGROUND

Materials generally used in bicycle tires for puncture resistanceinclude relatively high strength multifilament woven yarns of fibrousmaterials such as nylon, para-aramids (e.g., KEVLAR), and liquid crystalpolymers (e.g., VECTRAN). The individual filaments in the wovenmultifilament yarn fabrics can move laterally (i.e., side to sidebetween the side walls) as an object is forced between the filamentspiercing the fabric. While some foreign objects may be large enough soas not to be able to penetrate the weave of the polymeric fabric, otherforeign objects may exhibit dimensions that are relatively small,particularly in the lateral dimension, and may be more easily be forcedthrough the weave of the filaments and pierce the tire tube.

Aluminum and titanium foil strips have also been incorporated in bicycletires due to their relatively low densities, in an effort to keep theoverall weight of the tires low. However, aluminum is relatively soft.In addition, titanium, while relatively harder than aluminum, is ofrelatively greater expense, limiting its use. Still, these materials mayexhibit relatively low elasticity of approximately 0.2% (i.e. the amountof strain that the material may undergo without plastic deformation).The elastic limit of these metals may be overcome when hard impacts orforeign objects are encountered and plastic deformation of the metalsmay reduce ride performance and durability of the tire. Accordingly,there remains a need to provide a puncture resistant tire that preventsforeign objects of various sizes from penetrating the tire and piercingthe tire tube.

SUMMARY

A tire is provided comprising a tire body, a metal reinforcing stripcomprising at least one metal alloy foil layer to provide punctureresistance, wherein the at least one metal alloy foil layer comprises aspinodal glass matrix microconstituent structure. The tire may be abicycle tire.

The tire may further comprise a tire body, and a metal reinforcing stripcomprising at least one metal alloy foil layer to provide punctureresistance, wherein the at least one metal alloy foil layer comprises aspinodal glass matrix microconstituent structure characterized by thepresence of two or more metal compositions separated into distinctphases with different chemical compositions and the phases include oneor more semicrystalline clusters having a largest linear dimension of 2nm or less and one or more crystalline clusters having a largest lineardimension of greater than 2 nm.

In certain embodiments, the metal alloy may comprise an Fe based alloyincluding Fe at a level of greater than 35-92 atomic percent, Ni at alevel of 4-40 atomic percent, B at a level of 7-25 atomic percent. Inother embodiments, the metal alloy may comprise an Fe based alloyincluding Fe at a level of greater than 35-92 atomic percent, Ni at alevel of 4-40 atomic percent, B at a level of 7-25 atomic percent, Si ata level of 0.3-8 atomic percent and Cr at a level of 0.1-25 atomicpercent.

In certain embodiments, the at least one metal alloy foil layer mayinclude metallic glass and the size of the structural units in themetallic glass in the range of 5 Angstroms to 100 Angstroms.

In certain embodiments, the spinodal glass matrix microconstituentstructure may be present in a range of 5% to 95% by volume of the metalalloy foil layer.

In certain embodiments, the at least one metal alloy foil layer may beprovided by a metal alloy composition having at least one of thefollowing properties: microhardness in a range of 850 HV to 950 HV; apercent elongation at break at a strain rate of 0.001 s⁻¹ in a range of1.5% to 5.0%; a moduli of elasticity at a strain rate of 0.001 s⁻¹ in arange of 140 GPa to 170 GPa; an ultimate tensile strength at a strainrate of 0.001 s⁻¹ in a range of 1500 MPa to 3000 MPa; and a yieldstrength at a strain rate of 0.001 s⁻¹ in a range of 1200 MPa to 2000MPa.

In certain embodiments, the metal reinforcing strip may comprise aplurality of metal alloy foil layers. The plurality of metal alloy foillayers may comprise a plurality of metal alloy foil layers which eachcomprise a spinodal glass matrix microconstituent structure.

In certain embodiments, the metal reinforcing strip may be arrangedaround a circumference of the tire body. The metal reinforcing strip maybe located underneath a tread of the tire body, or embedded in the tirebody. The metal reinforcing strip may be positioned on an inner surfaceof the tire body. The metal foil has a thickness in a range of 0.01 mmto 0.1 mm.

In certain embodiments, a method of providing a tire may compriseproviding a tire body; and providing a metal reinforcing stripcomprising at least one metal alloy foil layer to provide punctureresistance, wherein the at least one metal alloy foil layer comprises aspinodal glass matrix microconstituent structure characterized by thepresence of two or more metal compositions separated into distinctphases with different chemical compositions and the phases include oneor more semicrystalline clusters having a largest linear dimension of 2nm or less and one or more crystalline clusters having a largest lineardimension of greater than 2 nm; and wherein the metal reinforcing stripis embedded in the tire body.

In certain embodiments, a method of providing a tire may compriseproviding a tire body; and providing a metal reinforcing stripcomprising at least one metal alloy foil layer to provide punctureresistance, wherein the at least one metal alloy foil layer comprises aspinodal glass matrix microconstituent structure characterized by thepresence of two or more metal compositions separated into distinctphases with different chemical compositions and the phases include oneor more semicrystalline clusters having a largest linear dimension of 2nm or less and one or more crystalline clusters having a largest lineardimension of greater than 2 nm; and wherein the metal reinforcing stripis positioned on an inner surface of the tire body.

BRIEF DESCRIPTION OF DRAWINGS

The above mentioned and other features of this disclosure, and themanner of attaining them, may become more apparent and better understoodby reference to the following description of embodiments describedherein taken in conjunction with the accompanying drawings, wherein:

FIG. 1 illustrates a cross-sectional view of one embodiment of a tireconstruction including a metal foil embedded in the tire;

FIG. 2 illustrates a cross-sectional view of another embodiment of atire construction including a metal foil disposed between the tire andtube;

FIG. 3 illustrates a cross-sectional view of an embodiment of a tireperpendicular to the axis of rotation including a number of metal alloyfoil layers in a metal alloy strip;

FIG. 4 illustrates an embodiment of a metal alloy strip including wearresistant coating layers; and

FIG. 5 illustrates another embodiment of a metal alloy strip includingwear resistant coating layers.

DETAILED DESCRIPTION

The present application relates to a puncture resistant bicycle tire.The bicycle tire may incorporate a strip of one or more layers of metalalloy foil exhibiting spinodal glass matrix microconstituents. In someembodiments, the metal alloy foil strip may either be embedded withinthe tire or between the tire and tube.

FIG. 1 illustrates a cross-section of an embodiment of a bicycle wheelincluding one or more layers of a metal alloy foil, described furtherherein, embedded in the bicycle tire. As illustrated the wheel 10includes a tire 12 having a tire body 18 affixed to a wheel rim 14.Retained within the wheel rim 14 and the tire 12 is the tube 16. Thetire body 18 of the tire 12 may include retention features 22 a, 22 b,such as beads and embedded cords, for retaining the tire 12 within thewheel rim 14.

A metal alloy foil strip 24 may be embedded within the tire body 18 ofthe tire 12 underneath the inner surface 26 of the tire. The metal alloyfoil strip 24 may be provided along a portion 28 of the tire 12 that maybe most apt to touching the ground or another surface, as illustrated.The metal foil strip 24 may also extend proximate to the wheel rim onone or both sides of the tire 12 to a location 30 a, 30 b adjacentretention features 22 a, 22 b along the side walls 32 a, 32 b. Inaddition, tread 34 may be provided near the “contact surface” 28 of thetire. The tread 34 may either be integral to the body 18 of the tire 12or may be a second piece thermally, chemically and/or mechanicallyaffixed to the body 18 of the tire 12.

FIG. 2 illustrates a cross-section of another embodiment of a bicyclewheel including one or more layers of a metal alloy foil, describedfurther herein, positioned on the inner surface of the bicycle tire. Asillustrated, the wheel 10 includes a tire 12 affixed to a wheel rim 14.Retained within the wheel rim 14 and the tire 12 is the tube 16. Thetire body 18 of the tire 12 may include retention features 22 a, 22 bfor retaining the tire 12 within the wheel rim 14. A metal alloy foilstrip 24 may be retained on the inner surface 26 the tire body 18 of thetire 12. The metal alloy foil strip 24 may be provided along a portion28 of the tire 12 that may be most apt to touching the ground or anothersurface, as illustrated, or may extend proximate to the wheel rim on oneor both opposing sides of the tire 12 to a location 30 a, 30 b adjacentretention features 22 a, 22 b along the side walls 32 a, 32 b. In someembodiments, the metal alloy strip 24 may be positioned between theinner surface 26 of the tire body 18 of tire 12 and the tube 16, whereinthe metal alloy strip 24 may be retained by the pressure asserted by thetube 16 against the tire body 18 of tire 12 when the tube 16 isinflated.

In other embodiments, the metal alloy foil strip 24 may be retained onthe inner surface 26 by an adhesive or an adhesive tape applied betweenthe foil strip 24 and the inner surface 26. An adhesive tape may also beprovided over the metal foil strip 24, such that the tube 16 contactsthe adhesive tape rather than the metal foil strip 24. In furtherembodiments the metal alloy foil strip 24 may be retained on the innersurface 26 of the tire body 18 of tire 12 by a mechanical retainer, suchas a lip, that may surround a portion of the perimeter of the foil strip24. In addition, tread 34 may be provided near the “contact surface” 28of the tire. The tread 34 may either be integral to the body 18 of thetire 12 or may be a second piece thermally, chemically and/ormechanically affixed to the body 18 of the tire 12.

The metal alloy foil strips may be formed from metal alloy compositionsthat exhibit spinodal glass matrix microconstituents, which includesmetallic glasses. Spinodal Glass Matrix Microconstituent (i.e. SGMM) mayenable the achievement of ductility (≧1% elongation) arising from theability to blunt moving shear bands (i.e. ISBB) through specificmicrostructural interactions at the nanoscale called LocalizedDeformation Induced Changes (LDIC). Subsequent second level and higherarresting shear band interactions (SBAI), may allow the achievement ofrelatively high shear band densities under unconstrained loading and maylead to increased levels of global plasticity. Moreover, the result ofthis SBAI may include the development of a strain hardening effect whichmeans that the active ductility mechanisms may be usable and relevant toindustrial processing and applications where defects and the associatedstress concentration sites will always be present. The chemistriesdescribed herein may achieve the formation of spinodal glass matrixmicroconstituents at a relatively lower cost and may therefore enhancethe price/performance benefits to enable an expanded range of commercialmarkets for materials that include spinodal glass matrixmicroconstituents.

Accordingly, the metal alloy compositions for forming the metal alloyfoil strips may include glass forming chemistries which may lead toSpinodal Glass Matrix Microconstituent (SGMM) structures, which mayexhibit relatively significant ductility and high tensile strength.Spinodal glass matrix microconstituents may be understood asmicroconstituents formed by a transformation mechanism that is notnucleation controlled. More basically, spinodal decomposition may beunderstood as a mechanism by which a solution of two or more components(e.g. metal compositions) of the alloy can separate into distinctregions (or phases) with distinctly different chemical compositions andphysical properties. This mechanism differs from classical nucleation inthat phase separation occurs uniformly throughout the material and notjust at discrete nucleation sites. The phases may include one or moresemicrystalline clusters or crystalline phases, which may therefore formthrough a successive diffusion of atoms on a local level until thechemistry fluctuations lead to at least one distinct crystalline phase.Semi-crystalline clusters may be understood herein as exhibiting alargest linear dimension of 2 nm or less, whereas crystalline clustersmay exhibit a largest linear dimension of greater than 2 nm. Note thatduring the early stages of the spinodal decomposition, the clusterswhich are formed may be relatively small and while their chemistrydiffers from a surrounding glass matrix, they are not yet fullycrystalline and have not yet achieved well ordered crystallineperiodicity. Additional crystalline phases may exhibit the same crystalstructure or distinct structures.

Furthermore, as noted, the phases may include a glass matrix or metallicglass. Metallic glass may be understood to include microstructures thatmay exhibit associations of structural units in the solid phase that maybe randomly packed together. The level of refinement, or the size, ofthe structural units in the glass phase may be in the angstrom scalerange (i.e. 5 Å to 100 Å). Metallic glasses may be understood as arelatively unique class of materials that may exhibit characteristicswhich are both metal like, (since they may contain non-directionalmetallic bonds, metallic luster, and/or relatively significantelectrical and thermal conductivity), and ceramic like (since relativelyhigh hardness may often be exhibited coupled with brittleness and thelack of tensile ductility). Metallic glasses may be understood toinclude supercooled liquids that exist in solid form at room temperaturebut which may have structures that are similar to what is found in theliquid with only short range order present. Metallic glasses maygenerally have free electrons, exhibit metallic luster, and exhibitmetallic bonding similar to what is found in conventional metals.Metallic glasses may be metastable materials and when heated up, theymay transform into a crystalline state. The process is calledcrystallization or devitrification. Since diffusion is limited at roomtemperature, enough heat (i.e. Boltzman's Energy) may be applied toovercome the nucleation barrier to cause a solid-solid statetransformation which is caused by glass devitrification.

The devitrification temperature of metallic glasses can vary widely andmay be, for example, in the range of 300° C. to 800° C. with enthalpiesof crystallization commonly from −25 J/g to −250 J/g. Thedevitrification process can occur in one or multiple stages. Whenoccurring in multiple stages, a crystalline phase may be formed and thendepending on the specific partition coefficient, atoms may either beattracted to the new crystallites or rejected into the remaining volumeof the glass. This may result in more stable glass chemistry which maynecessitate additional heat input to cause partial or fulldevitrification. Thus, partially devitrified structures may result incrystalline precipitates in a glass matrix. Commonly, these precipitatesmay be in the size range of 30 nm to 125 nm. Full devitrification to acompletely crystalline state may result from heat treating above thehighest temperature glass peak which can be revealed through thermalanalysis such as differential scanning calorimetry or differentialthermal analysis.

The relatively fine length scale of the structural order, (i.e.molecular associations), and near defect free nature of the material,(i.e. no 1-d dislocation or 2-d grain/phase boundary defects), mayprovide relatively high strength, (and corresponding hardness), whichmay be on the order of 33% to 45% of theoretical. However, due to thelack of crystallinity, dislocations may not be found and a mechanism forsignificant (i.e. >1%) tensile elongation may not be apparent. Metallicglasses may exhibit limited fracture toughness associated with therelatively rapid propagation of shear bands and/or cracks which may be aconcern for the technological utilization of these materials. Whilethese materials may show adequate ductility when tested in compression,when tested in tension they exhibit elongation very close to zero andfracture in the brittle manner. The inherent inability of these classesof materials to deform in tension at room temperature may be a limitingfactor for all potential structural applications where intrinsicductility is needed to avoid catastrophic failure. Owing to strainsoftening and/or thermal softening, plastic deformation of metallicglasses may be relatively highly localized into shear bands, resultingin a limited plastic strain (exhibiting less than 1% elongation) andcatastrophic failure at room temperature.

In addition, the spinodal glass matrix microconstituent (SGMM) mayenable the metal alloys herein to exhibit Induced Shear Band Blunting(ISBB) and Shear Band Arresting Interactions (SBAI). ISBB may beunderstood as the ability to blunt and stop propagating shear bandsthrough interactions with the SGMM structure. SBAI may be understood asthe arresting of shear bands through shear band/shear band interactionsand may occur after the initial or primary shear bands are bluntedthrough ISBB.

While conventional materials may deform through dislocations moving onspecific slip systems in crystalline metals, ISBB and SBAI deformationmechanisms may involve moving shear bands (i.e., discontinuities wherelocalized deformation occurs) in a spinodal glass matrixmicroconstituent, which are blunted by localized deformation inducedchanges (LDIC) described further herein. With increasing levels ofstress, once a shear band is blunted, new shear bands may be nucleatedand then interact with existing shear bands creating relatively highshear band densities in tension and the development of relativelysignificant levels of global plasticity. Thus, the alloys with favorableSGMM structures may prevent or mitigate shear band propagation intension, which may result in relatively significant tensile ductility(>1%) and lead to strain hardening during tensile testing. The alloyscontemplated herein may include or consist of chemistries capable offorming a spinodal glass matrix microconstituent, wherein the spinodalglass matrix microconstituents may be present in the range of 5 to 95%by volume, including glassy, semi-crystalline, and/or crystallinephases.

Glass forming chemistries that may be used to form the metal alloysincluding the spinodal glass matrix microconstituent structures hereinmay include certain iron based glass forming alloys, which are thenprocessed to provide the SGMM structures noted herein. The iron basedalloys may include iron present at levels of greater than 35 atomic %.In addition, the alloys may include the elements iron, nickel, boron. Insome embodiments, the alloys may include, be limited to, or consistessentially of iron, nickel, boron, and cobalt. In some embodiments, thealloys may include, be limited to, or consist essentially of iron,nickel, boron, cobalt, and silicon. In some embodiments, the alloys mayinclude, be limited to, or consist essentially of iron, nickel, boron,cobalt, carbon and silicon. In further embodiments, the above alloys mayalso include one or more of chromium, titanium, molybdenum, aluminum,copper, cerium, tungsten, chromium and yttrium.

In some embodiments, iron may be present in the range of 35 atomicpercent to 92 atomic percent, including all values and ranges therein,such as individual values and ranges selected from 40 atomic percent to70 atomic percent. Nickel may be present from 4 atomic percent to 40atomic percent, including all values and ranges therein, such asindividual values and ranges selected from 4 atomic percent to 30 atomicpercent, 10 to 30 atomic percent or 13 atomic percent to 17 atomicpercent. Boron may be present in the range of 7 atomic percent to 25atomic percent, including all values and ranges therein, such asindividual values and ranges selected from 10 atomic percent to 19atomic percent or 12 atomic percent to 17 atomic percent. Cobalt, whenpresent, may be present in the range of 1 atomic percent to 21 atomicpercent, including all values and ranges therein, such as values andranges selected from 2 atomic percent to 12 atomic percent or 1 atomicpercent to 5 atomic percent. Carbon, when present, may be present in therange of 0.1 atomic percent to 6 atomic percent including all values andranges therein, such as values and ranges selected from 1 atomic percentto 5 atomic percent. Silicon, when present, 0.3 atomic percent to 8atomic percent including all values and ranges therein, such as valuesand ranges selected from 0.4 atomic percent to 4 atomic percent.Titanium, when present, may be present up to 25 atomic percent,including all values and ranges therein, such as values and rangesselected from 1 atomic percent to 20 atomic percent or 1 atomic percentto 8 atomic percent. Molybdenum, when present, may be present up to 25atomic percent, including all values and ranges therein, such as valuesand ranges selected from 1 atomic percent to 20 atomic percent or 1atomic percent to 8 atomic percent. Aluminum, when present, may bepresent up to 25 atomic percent, including all values and rangestherein, such as values and ranges selected from 1 atomic percent to 20atomic percent or 2 atomic percent to 16 atomic percent. Copper, whenpresent, may be present up to 25 atomic percent, including all valuesand ranges therein, such as values and ranges selected from 1 atomicpercent to 25 atomic percent. Cerium, when present, may be present from1 atomic percent to 8 atomic percent, including all values and rangestherein. Tungsten, when present, may be present up to 25 atomic percent,including all values and ranges therein, such as individual values andranges selected from 0.1 atomic percent to 25 atomic percent. Chromium,when present, may be present up to 25 atomic percent, including allvalues and ranges therein, such as 0.1 atomic percent to 25 atomicpercent or 2 atomic percent to 3 atomic percent. Yttrium, when present,may be present up to 25 atomic percent, including all values and rangestherein, such as from 0.1 atomic percent to 25 atomic percent.

Alloy Fe Ni B Si Cr Alloy 1 64.97 16.49 14.99 0.46 3.09 Alloy 2 62.8310.00 13.40 0.42 13.35

Due to, for example, the purity of the feedstock and introduction ofimpurities during processing, the alloys may include up to 3 atomicpercent of impurities. In addition, the above described iron based alloycompositions described above may be present in the range of 90 atomicpercent to 100 atomic percent of a larger metal alloy composition,including all values and increments therein, such as in the range of 90atomic percent to 99 atomic percent, etc.

While not intended to be limiting, an analysis of the mechanisms ofdeformation appear to show that that the operating mechanisms for ISBBand SBAI are orders of magnitude smaller than the system size. Theoperable system size may be understood as the volume of materialcontaining the SGMM structure, which again may be in the range of 5% to95% by volume. Additionally, for a liquid melt cooling on a chillsurface such as a wheel or roller (which can be as wide as engineeringwill allow) 2-dimensional cooling may be a predominant factor inspinodal glass matrix microconstituent formation, thus the thickness maybe a limiting factor on structure formation and resulting operablesystem size. At thicknesses above a reasonable system size compared tothe mechanism size, the ductility mechanism may be unaffected. Forexample, the shear band widths may be relatively small (10 to 100 nm)and even with the LDIC interactions with the structure the interactionsize may be from 20 to 200 nm. Thus, for example, achievement ofrelatively significant ductility (≧1%) at a 100 micron thickness meansthat the system thickness is already 500 to 10,000 times greater thanductility mechanism sizes.

It is contemplated that the operable system size, which when exceededwould allow for ISBB and SBAI interactions, may be in the range of ˜10nm to 1 micron in thickness or 1000 nm³ to 1 μm³ in volume. Achievingthicknesses greater ˜1 micron or operable volumes greater 1 μm³ may notbe expected to significantly affect the operable mechanisms orachievement of significant levels of plasticity since the operableductility mechanistic size is below this limit. Thus, greater thicknessor greater volume samples or products would be contemplated to achievean operable ductility with ISBB and SBAI mechanisms in a similar fashionas identified as long as the SGMM structure is formed.

Manufacturing of the metal alloy foil may be performed using techniquesthat may result in cooling rates sufficient to provide the SGMMstructures. Such cooling rates may be in the range of 10³ to 10⁶ K/s.Examples of processing techniques that may be configured to provide theSGMM structures herein and associated plasticity may include, but arenot limited to, melt-spinning/jet casting, planar flow casting, and twinroll casting. Additional details of these manufacturing techniques,operating in a manner to provide the structures and resulting propertiespresented in this application herein, are included below.

Melt spinning may be understood to include a liquid melt ejected usinggas pressure onto a rapidly moving copper wheel. Continuous or broken uplengths of ribbon may be produced. In some embodiments, the ribbon maybe in the range of 1 mm to 2 mm wide and 0.015 to 0.15 mm thick,including all values and increments therein. The width and thickness maydepend on the melt spun materials viscosity and surface tension and thewheel tangential velocity. Typical cooling rates in the melt-spinningprocess may be from ˜10⁴ to ˜10⁶ K/s, including all values andincrements therein. Ribbons may generally be produced in a continuousfashion up to 25 m long using a laboratory scale system.

Jet casters may be used to melt-spin alloys on a commercial scale.Process parameters in one embodiment of melt spinning may includeproviding the liquid melt in a chamber, which is in an environmentincluding air or an inert gas, such as helium, carbon dioxide, carbondioxide and carbon monoxide mixtures, or carbon dioxide and argonmixtures. The chamber pressure may be in the range of 0.25 atm to 1 atm,including all values and increments therein. Further, the casting wheeltangential velocity may be in the range of 15 meters per second (m/s) to30 m/s, including all values and increments therein. Resulting ejectionpressures may be in the range of 100 to 300 mbar and resulting ejectiontemperatures may be in the range of 1000° C. to 1300° C., including allvalues and increments therein.

Planar flow casting may be understood as a relatively low cost andrelatively high volume technique to produce wide ribbon in the form ofcontinuous sheet. The process may include flowing a liquid melt at aclose distance over a chill surface. Widths of thin foil/sheet up to18.4″ (215 mm), including all values and increments in the range of 10mm to 215 mm, may be produced on a commercial scale with thickness inthe range of 0.016 to 0.075 mm, including all values and incrementstherein. Cooling rates in the range of ˜10⁴ to ˜10⁶ K/s, including allvalues and increments therein may be provided. After production ofsheets, the individual sheets (from 5 to 50) may be warm pressed to rollbond the compacts into sheets.

Twin roll casting may be understood to include quenching a liquid meltbetween two rollers rotating in opposite directions. Solidification maybegin at first contact between the upper part of each of the rolls andthe liquid melt. Two individual shells may begin to form on each chillsurface and, as the process continues, may be subsequently broughttogether at the roll nip by the chill rolls to form one continuoussheet. In this approach, solidification may occur rapidly and directmelt thicknesses may be achieved much thinner than conventional meltprocesses and typically into the 1.5 mm to 3.0 mm range prior to anypost processing steps such as hot rolling. The process may be similar inmany ways to planar flow casting, yet a main difference is that twochill rollers may used to produce sheet in twin roll casting rather thana single chill roller in planar flow casting. However, in the context ofthe sheet that may be produced herein, having the indicated SGMMstructure, the thickness may be in the range of 0.5 mm to 5.0 mm.

The metal alloys may exhibit a density, in ingot form as measured by theArchimedes method, in the range of 7.0 grams/cubic centimeter to 8.0grams/cubic centimeter, including all values and ranges therein. Themetal alloys may exhibit a relatively high microhardness of 850 HV orgreater. In some embodiments, the microhardness may be in the range of850 HV to 950 HV including all values and ranges therein, such as 900HV. Microhardness may be understood as hardness measured using a Vickersindenter at a constant load of 50 g with at least 10 measurements persample.

The metal alloy may exhibit an ultimate tensile strength of 1500 MPa orgreater. In some embodiments, the metal alloys may exhibit an ultimatetensile strength in the range of 1500 MPa to 3000 MPa, including allvalues and ranges therein, at a strain rate of 0.001 s⁻¹. The metalalloys may also exhibit yield strength of 1200 MPa or greater. In someembodiments, the yield strength may be in the range of 1200 MPa to 2000MPa, including all values and ranges therein, such as 1.3 GPa, at astrain rate of 0.001 s⁻¹. The metal alloys may further exhibit a percentelongation at break of 1.5% or greater. In some embodiments, the percentelongation may be in the range of 1.5% to 5.0%, including all values andincrements therein, at a strain rate of 0.001 s⁻¹. Further, the modulusof elasticity of these materials may be in the range of 140 GPa to 170GPa, including all values and ranges therein, at a strain rate of 0.001s⁻¹. These mechanical properties of the metallic ribbons may bedetermined at room temperature using microscale tensile testing. Thetesting may be carried out in a commercial tensile stage made by ErnestFullam Inc. which was monitored and controlled by a MTEST Windowssoftware program, or using similar testing set-ups. The deformation maybe applied by a stepping motor through the gripping system while theload was measured by a load cell that was connected to the end of onegripping jaw. Displacement may be obtained using a Linear VariableDifferential Transformer (LVDT) which was attached to the two grippingjaws to measure the change of gage length. Before testing, the thicknessand width of a ribbon tensile specimen may be carefully measured atleast three times at different locations in the gage length. The averagevalues may then be recorded as gage thickness and width, and used asinput parameters for subsequent stress and strain calculation. Theinitial gage length for tensile testing may be set at ˜7 to ˜9 mm withthe exact value determined after the ribbon was fixed, by accuratelymeasuring the ribbon span between the front faces of the two grippingjaws. All tests may be performed under displacement control, with astrain rate of ˜0.001 s⁻¹. Elastic strain, total elongation, yieldstrength, ultimate tensile strength, and Young's Modulus may becalculated by a MTEST Windows software program at each test. The thermalconductivity of the metal alloys may be in the range of 5 W/m*K to 25W/m*K, including all values and ranges therein, and the coefficient ofthermal conductivity may be in the range of 12 micrometers per meter oflength (ppm)/° C. to 15 ppm/° C.

Once the foils are formed, one or more metal alloy foils may be providedto form the metal alloy strips. The total thickness of the metal alloystrip including one or more metal foil layers may be in the range of0.010 mm to 0.100 mm in thickness, including all values and rangestherein, such as a thickness selected from the range of 0.010 mm to0.070 mm. Where more than one foil layer may be provided, each layer maybe 0.010 to 0.050 mm in thickness, including all values and rangestherein. In addition, where more than one foil layer is present, 2 ormore foil layers may be present. Multiple foil layers may be adheredtogether forming a laminate. Metal alloy strips of the metal alloysdescribed herein may be incorporated into the wheel, as illustrated inFIGS. 1 and 2, wherein the metal alloys strip may be embedded within thetire or may be positioned on the inner surface of the tire.

In some embodiments, the metal alloy strip may be continuous around thecircumference of the tire. Where multiple layers of foil may be present,as illustrated in FIG. 3, the meeting location of the ends 36 a, 36 b,36 c of the foils 38 a, 38 b, 38 c in the strip 24 may be spaced apartso that all of the ends of all the foil layers do not fall at the samelocation on the tire 12. In other embodiments, the metal alloy strip maybe a series of discontinuous strips applied at various intervals aroundthe inner circumference of the tire. The discontinuous strips mayoverlay or may be spaced apart. In addition, as alluded to above, themetal alloy strip may be formed from one layer or from multiple layersstacked together to form a laminate. Adhesive materials maybe appliedbetween the various laminate layers or the layers may be otherwisetacked or bonded together.

In some embodiments, where the metal alloy strip 24 is embedded in thetire body 18 of tire 12, as illustrated in FIG. 1, the strip may beincorporated into the tire when the tire is being formed. For example,the composition forming the tire body 18 may be formed around the strip24, embedding the strip 24 within the tire body 18. In another example,the metal strip may be placed between two portions of the tire and thetire may be affixed together. A first portion of the tire may be formed,the strip may be placed on the first portion and a second portion of thetire may be provided or formed over the strip and/or the first portionof the tire embedding the strip between the two portions. Adhesive maybe applied to the strip or first portion of the tire to retain the stripbefore the second portion of the tire is formed or adhesive may beapplied the second portion of the tire.

In other embodiments, where the metal alloy strip is retained betweenthe tire and the tube, as illustrated in FIG. 2, the tire may be firstmolded and then the strip may be positioned on the inner surface of thetire body 18 of tire 12. An adhesive may be applied to retain the strip.The adhesive may be applied between the tire and the strip as a liquidor a gum or may be applied as adhesive tape over the strip, contactingthe tire around the periphery of the metal alloy strip.

The metal strip may also be treated or otherwise functionalized toimprove the adhesion between the metal strip and the composition formingthe tire. For example, a coating may be applied to the metal strip. Thecoating may include silane compositions, such as those disclosed indisclosed in U.S. Application No. 2010/0291382, the teachings of whichare incorporated herein by reference. Other compositions may includemetal salts of acrylic and methacrylic acids; multifunctional monomers,such as diacrylates, dimethacrylated and monomethacrylates, which may beavailable, for example, from Cray Valley, of Exton, Pa.

One or more wear resistant layers may also be provided to prevent themetal alloy strip from wearing into the tire, the tube or both. FIG. 4illustrates an example of wear resistant layers 40, 42 formed over themetal alloy strip 24. Adhesive layers 44, 46 may be provided between thewear resistant layers 40, 42 to chemically or mechanically bond themetal alloys strip 24 to the wear resistant layers 40, 42 as is shown inFIG. 5. The wear resistant layers may be formed from films includingfilms formed from thermoplastic materials or woven fabric or nonwovenfabrics formed from natural fibers, synthetic fibers or both.Thermoplastic materials may include polyolefins such as polyethylene orpolypropylene, fluoropolymers, polyester, polyether ether ketone, etc.Natural fibers may include cotton, cellulose, etc. Synthetic fibers mayinclude polyolefin fibers such as polyethylene fibers, polypropylenefibers, polyester fibers, aramid fibers, etc. The one or more wearresistant layers may be disposed over the metal alloy strip prior toincorporating the metal alloy strip into the tire, or the layers may beprovided while incorporating the metal alloy strip into the tire.

In some embodiments, the wear resistant layers may be heat sealed overthe metal alloy strip, around at least a portion of the periphery of themetal alloy strip, or around the entire periphery of the metal alloystrip. In such a manner, pressure and/or thermal energy may be providedto melt the wear resistant layers sufficient to get partial to completemelting of the films or fibers. A portion of the film or fiber of onewear resistant layer may commingle with the film or fiber of anotherwear resistant layer forming mechanical or chemical bonds.

As may be appreciated, the relatively high hardness of the metal alloyfoil may further reduce the penetration of foreign objects, regardlessof the dimensions of the foreign objects, as the strip may be unitaryfrom side wall to side wall. In addition, relatively sharp foreignobjects may be dulled when forced into the surface of the metal alloyfoils, reducing the ability of the object to pierce the foil. Thus, therelatively thin metal foil may provide a relatively light weightsolution to puncture resistance.

The metal alloy reinforcing strip may also reduce rolling resistance.Rolling resistance may be understood as resistance that occurs when around object rolls on a flat surface. Rolling resistance may be causedby the deformation of the object, the surface or both. In rubber tires,hysteresis exhibited by the materials may be understood as acontributing factor to rolling resistance. It is contemplated that themetal alloy strip may reduce the deformation in the tire duringrotation, thereby reducing rolling resistance, while still maintainingsome degree of dampening (i.e. reduction in transfer of vibrations).Accordingly, the use of the metal alloy reinforcing strip of the presentdisclosure containing SGMM structure such as hardness values of 850 HVto 950 HV and percent elongations of 1.5% to 5.0% with moduli ofelasticity of 140 GPa to 170 GPa provided unexpected advantages withinthe tire during rotational motion.

Furthermore, increased weight may also contribute to rolling resistanceand, therefore, the reduced weight of the strip may also reduce rollingresistance. Bicycle tires of the present disclosure may exhibit thefollowing typical tire weights included below in Table 1.

TABLE 1 Typical Tire Weights ISO tire Weight savings diameter Weightrange [g] using Tire type [mm] [g], typical SGMM Road racing 622 180-2201-12 Road city/touring 622 400-700 1-12 Mountain slick/semi-slick 559550-850 3-25 Mountain cross-country 559 500-700 3-25 BMX 406 500-6502-20

Thus, the relatively thin metal foil including SGMM may provide a lightweight solution to puncture resistance, which may also reduce therolling resistance.

EXAMPLES

The examples herein are presented for purposes of illustration and arenot meant to limit the scope of the description and claims appendedhereto.

Example 1

Table 2 provides a comparison of the difference in weight between themetal alloys described herein and examples of alternative materialsaimed at increasing puncture resistance. Samples 1 through 4 aredirected to the metal alloy strips at one inch widths. Samples 5 through9 include the compositions described in WO 02/18158. Samples 10 and 11include woven VECTRAN and aramid fibers (available from SPINSKINS underthe model name RACE) and woven industrial fibers (again available fromSPINSKINS under the model name DURO). Samples 12 through 15 includealuminum and polyurethane at a one inch width as described in U.S. Pat.No. 6,877,637. The weight is that of a strip material that may beemployed in a typical tire, i.e., a 700 centimeter diameter tire (ISO23-622). The SGMM foil in Table 2 corresponds to Alloy 1 noted above.

TABLE 2 Weight Comparison Foil Thickness Weight Sample Material [mm][g/m²] 1 SGMM foil 0.020 156 2 SGMM foil 0.030 234 3 SGMM foil 0.040 3124 SGMM foil 0.050 390 5 Example 1 Fabric (WO 02/18158) 320 6 Example 2Fabric (WO 02/18158) 224 7 Example 3 Fabric (WO 02/18158) 216 8 Example4 Fabric (WO 02/18158) 485 9 Example 5 Fabric (WO 02/18158) 659 10SpinSkins Race 0.737 310 11 SpinSkins Duro 0.559 374 12 Aluminum + 0.13mm thick 0.305 581 polyurethane per side 13 Aluminum + 0.13 mm thick0.356 719 polyurethane per side 14 Aluminum + 0.13 mm thick 0.457 994polyurethane per side 15 Aluminum + 0.13 mm thick 0.660 1545polyurethane per side

It may be appreciated that a metal alloy foil strip with a thicknessless than 0.0275 mm may exhibit a lower weight than any of the othermaterials shown in the table above.

What is claimed is:
 1. A tire comprising: a tire body; and a metalreinforcing strip comprising at least one metal alloy foil layer toprovide puncture resistance, wherein the at least one metal alloy foillayer comprises a spinodal glass matrix microconstituent structurecharacterized by the presence of two or more metal compositionsseparated into distinct phases with different chemical compositions andthe phases include one or more semicrystalline clusters having a largestlinear dimension of 2 nm or less and one or more crystalline clustershaving a largest linear dimension of greater than 2 nm.
 2. The tire ofclaim 1 wherein: the metal alloy comprises an Fe based alloy includingFe at a level of greater than 35-92 atomic percent, Ni at a level of4-40 atomic percent, B at a level of 7-25 atomic percent.
 3. The tire ofclaim 1 wherein: the metal alloy comprises an Fe based alloy includingFe at a level of greater than 35-92 atomic percent, Ni at a level of4-40 atomic percent, B at a level of 7-25atomic percent, Si at a levelof 0.3-8 atomic percent and Cr at a level of 0.1-25 atomic percent. 4.The tire of claim 1 wherein: the at least one metal alloy foil layerincludes metallic glass and the size of the structural units in themetallic glass in the range of 5 Angstroms to 100 Angstroms.
 5. The tireof claim 1 wherein: the spinodal glass matrix microconstituent structureis present in a range of 5% to 95% by volume of the metal alloy foillayer.
 6. The tire of claim 1 wherein: the at least one metal alloy foillayer is provided by a metal alloy composition having a microhardness ina range of 850 HV to 950 HV.
 7. The tire of claim 1 wherein: the atleast one metal alloy foil layer is provided by a metal alloycomposition having a percent elongation at break at a strain rate of0.001 s⁻¹ in a range of 1.5% to 5.0%.
 8. The tire of claim 1 wherein:the at least one metal alloy foil layer is provided by a metal alloycomposition having a moduli of elasticity at a strain rate of 0.001 s⁻¹in a range of 140 GPa to 170 GPa.
 9. The tire of claim 1 wherein: atleast one metal alloy foil layer is provided by a metal alloycomposition, having an ultimate tensile strength at a strain rate of0.001 s⁻¹ in a range of 1500 MPa to 3000 MPa.
 10. The tire of claim 1wherein: at least one metal alloy foil layer is provided by a metalalloy composition having a yield strength at a strain rate of 0.001 s⁻¹in a range of 1200 MPa to 2000 MPa.
 11. The tire of claim 1 wherein: themetal reinforcing strip comprises a plurality of metal alloy foillayers.
 12. The tire of claim 11 wherein: the plurality of metal alloyfoil layers comprise a plurality of metal alloy foil layers which eachcomprise a spinodal glass matrix microconstituent structure.
 13. Thetire of claim 1 wherein: the metal reinforcing strip is arranged arounda circumference of the tire body.
 14. The tire of claim 1 wherein: themetal reinforcing strip is located underneath a tread of the tire body.15. The tire of claim 1 wherein: the metal reinforcing strip is embeddedin the tire body.
 16. The tire of claim 1 wherein: the metal reinforcingstrip is positioned on an inner surface of the tire body.
 17. The tireof claim 1 wherein: the metal foil has a thickness in a range of 0.01 mmto 0.1 mm.
 18. The tire of claim 1 further comprising: a bicycle tire.19. A method of providing a tire comprising: providing a tire body;providing a metal reinforcing strip comprising at least one metal alloyfoil layer to provide puncture resistance, wherein the at least onemetal alloy foil layer comprises a spinodal glass matrixmicroconstituent structure characterized by the presence of two or moremetal compositions separated into distinct phases with differentchemical compositions and the phases include one or more semicrystallineclusters having a largest linear dimension of 2 nm or less and one ormore crystalline clusters having a largest linear dimension of greaterthan 2 nm; and wherein the metal reinforcing strip is embedded in thetire body.
 20. A method of providing a tire comprising: providing a tirebody; providing a metal reinforcing strip comprising at least one metalalloy foil layer to provide puncture resistance, wherein the at leastone metal alloy foil layer comprises a spinodal glass matrixmicroconstituent structure characterized by the presence of two or moremetal compositions separated into distinct phases with differentchemical compositions and the phases include one or more semicrystallineclusters having a largest linear dimension of 2 nm or less and one ormore crystalline clusters having a largest linear dimension of greaterthan 2 nm; and wherein the metal reinforcing strip is positioned on aninner surface of the tire body.